Effect of surface oxidation on the electronic transport properties of phosphorene gas sensors: a computational study

The potential for phosphorene-based devices has been compromised by the material's fast degradation under ambient conditions. Its tendency to fully oxidize under O₂-rich and humid environments, leads to the loss of its appealing semiconducting properties. However, partially-oxidized phosphorene (po-phosphorene), has been demonstrated to remain stable over significantly longer periods of time, thereby enabling its use in sensing applications. Here, we present a computational study of po-phosphorene-based gas sensors, using the Density-Functional-based Tight Binding (DFTB) method. We show that DFTB accurately predicts the bandgap for the pristine material and po-phosphorene, the electronic transport properties of po-phosphorene at different surface oxygen concentrations, and the appropriate trends in Density-of-States (DOS) contributions caused by adsorbed gas molecules, to demonstrate its potential application in the development of gas sensors. Results are compared against the more traditional and expensive Density Functional Theory (DFT) method using generalized gradient approximation (GGA) exchange–correlation functionals, which significantly underestimates the material's bandgap

Nonadiabatic Study of Dynamic Electronic Effects during Brittle Fracture of Silicon

It has long been observed that brittle fracture of materials can lead to emission of high energy electrons and UV photons, but an atomistic description of the origin of such processes has lacked. We report here on simulations using a first-principles-based electron force field methodology with effective core potentials to describe the nonadiabatic quantum dynamics during brittle fracture in silicon crystal. Our simulations replicate the correct response of the crack tip velocity to the threshold critical energy release rate, a feat that is inaccessible to quantum mechanics methods or conventional force-field-based molecular dynamics. We also describe the crack induced voltages, current bursts, and charge carrier production observed experimentally during fracture but not previously captured in simulations. We find that strain-induced surface rearrangements and local heating cause ionization of electrons at the fracture surfaces

Reactive Molecular Dynamics Simulations to Understand Mechanical Response of Thaumasite under Temperature and Strain Rate Effects

Understanding the structural, thermal, and mechanical properties of thaumasite is of great interest to the cement industry, mainly because it is the phase responsible for the aging and deterioration of civil infrastructures made of cementitious materials attacked by external sources of sulfate. Despite the importance, effects of temperature and strain rate on the mechanical response of thaumasite had remained unexplored prior to the current study, in which the mechanical properties of thaumasite are fully characterized using the reactive molecular dynamics (RMD) method. With employing a first-principles based reactive force field, the RMD simulations enable the description of bond dissociation and formation under realistic conditions. From the stress–strain curves of thaumasite generated in the x, y, and z directions, the tensile strength, Young’s modulus, and fracture strain are determined for the three orthogonal directions. During the course of each simulation, the chemical bonds undergoing tensile deformations are monitored to reveal the bonds responsible for the mechanical strength of thaumasite. The temperature increase is found to accelerate the bond breaking rate and consequently the degradation of mechanical properties of thaumasite, while the strain rate only leads to a slight enhancement of them for the ranges considered in this study

General Multiobjective Force Field Optimization Framework, with Application to Reactive Force Fields for Silicon Carbide

First-principles-based force fields prepared from large quantum mechanical data sets are now the norm in predictive molecular dynamics simulations for complex chemical processes, as opposed to force fields fitted solely from phenomenological data. In principle, the former allow improved accuracy and transferability over a wider range of molecular compositions, interactions, and environmental conditions unexplored by experiments. That is, assuming they have been optimally prepared from a diverse training set. The trade-off has been force field engines that are functionally complex, with a large number of nonbonded and bonded analytical forms that give rise to rather large parameter search spaces. To address this problem, we have developed GARFfield (genetic algorithm-based reactive force field optimizer method), a hybrid multiobjective Pareto-optimal parameter development scheme based on genetic algorithms, hill-climbing routines and conjugate-gradient minimization. To demonstrate the capabilities of GARFfield we use it to develop two very different force fields: (1) the ReaxFF reactive force field for modeling the adiabatic reactive dynamics of silicon carbide growth from an methyltrichlorosilane precursor and (2) the SiC electron force field with effective core pseudopotentials for modeling nonadiabatic dynamic phenomena with highly excited electronic states. The flexible and open architecture of GARFfield enables efficient and fast parallel optimization of parameters from quantum mechanical data sets for demanding applications like ReaxFF, electronic fast forward (or electron force field), and others including atomistic reactive charge-optimized many-body interatomic potentials, Morse, and coarse-grain force fields

Development of a ReaxFF Reactive Force Field for Ettringite and Study of its Mechanical Failure Modes from Reactive Dynamics Simulations

Ettringite is a hexacalcium aluminate trisulfate hydrate mineral that forms during Portland cement hydration. Its presence plays an important role in controlling the setting rate of the highly reactive aluminate phases in cement paste and has also been associated with severe cracking in cured hardened cement. To understand how it forms and how its properties influence those of hardened cement and concrete, we have developed a first-principles-based ReaxFF reactive force field for Ca/Al/H/O/S. Here, we report on the development of this ReaxFF force field and on its validation and application using reactive molecular dynamics (RMD) simulations to characterize and understand the elastic, plastic, and failure response of ettringite at the atomic scale. The ReaxFF force field was validated by comparing the lattice parameters, pairwise distribution functions, and elastic constants of an ettringite crystal model obtained from RMD simulations with those from experiments. The predicted results are in close agreement with published experimental data. To characterize the atomistic failure modes of ettringite, we performed stress–strain simulations to find that Ca–O bonds are responsible for failure of the calcium sulfate and tricalcium aluminate (C3A) column in ettringite during uniaxial compression and tension and that hydrogen bond re-formation during compression induces an increase in plastic strain beyond the material’s stress–strain proportionality limit. These results provide essential insight into understanding the mechanistic role of this mineral in cement and concrete degradation, and the ReaxFF potential developed in this work serves as a fundamental tool to further study the kinetics of hydration in cement and concrete

Elucidation of the dynamics for hot-spot initiation at nonuniform interfaces of highly shocked materials

The fundamental processes in shock-induced instabilities of materials remain obscure, particularly for detonation of energetic materials. We simulated these processes at the atomic scale on a realistic model of a polymer-bonded explosive (3,695,375 atoms/cell) and observed that a hot spot forms at the nonuniform interface, arising from shear relaxation that results in shear along the interface that leads to a large temperature increase that persists long after the shock front has passed the interface. For energetic materials this temperature increase is coupled to chemical reactions that lead to detonation. We show that decreasing the density of the binder eliminates the hot spot

Large-scale Molecular Simulations of Hypervelocity Impact of Materials

We describe the application of the ReaxFF reactive force field with short-range distance-dependent exponential inner wall corrections and the non-adiabatic electron Force Field (eFF) for studying the hypervelocity impact (HVI) effects on material properties. In particular, to understanding nonequilibrium energy/mass transfer, high strain/heat rate material decomposition, defects formation, plastic flow, phase transitions, and electronic excitation effects that arise from HVI impact of soft and hard materials on different material surfaces. Novel results are presented on the single shock Hugoniot and shock chemistry of Nylon6-6, on the hypervelocity shock sensitivity of energetic materials with planar interfacial defects and on HVI chemistry of silicon carbide surfaces with diamondoid nanoparticles. Both methods provide a means to elucidate the chemical, atomic and molecular processes that occur within the bulk and at the surfaces of materials subjected to HVI conditions and constitute a critical tool to enabling technologies required for the next generation of energy, spatial, transportation, medical, and military systems and devices, among many others. This has proven to be extremely challenging, if not impossible, for experimental observations, mainly because the material states that occur are hard to isolate and their time scales for changes are too rapid (<1 ps). First principles quantum mechanics (QM) simulation methods have also been bounded by the prohibitive scaling cost of propagating the total Schrödinger equation for more than 100 atoms at finite temperatures and pressures

Ligand-Modified Boron-Doped Diamond Surface: DFT Insights into the Electronic Properties of Biofunctionalization

With the increasing power of computation systems, theoretical calculations provide a means for quick determination of material properties, laying out a research plan, and lowering material development costs. One of the most common is Density Functional Theory (DFT), which allows us to simulate the structure of chemical molecules or crystals and their interaction. In developing a new generation of biosensors, understanding the nature of functional linkers, antibodies, and ligands become essential. In this study, we used DFT to model a bulk boron-doped diamond slab, modified by a functional linker and a surrogate proteins ligand. DTF calculations enable the prediction of electronic transport properties in an electrochemical sensor setup, composed of a boron-doped diamond electrode functionalized by 4-amino benzoic acids and a target surrogated protein-ligand for influenza. Electron conduction pathways and other signatures associated with the detection and measurement of the target analyte are revealed